Chromable dyestuffs of the triarylmethane series and process of preparing them



Patented Nov. 19, 1940 uNrrEo STATE CHROMABLE DYESTUFFS OF THE TRIARYL- METHANE SERIES AND PROCESS OF PRE PARING THEE I Wilhelm Eckert and Karl Schilling, Frankfort-onthe-Main-Hochst, Germany, assignors to General Aniline & Film Corporation, a corporation of Delaware I No Drawing. Application September 13, 1938,

Serial No. 229,768. In

4 Claims.

The present invention relates to chromable dyestufis of the triarylmethane series and to a process of preparing them and is a continuationin-part of U. S Patent No. 2,133,780 issued Octo- 5 her 18, 1938 (application Serial No. 131,936, filed March 19, 1937, for: Chromable dyestuffs of the triarylmethane series and process of preparing them in the name of Wilhelm Eckert and Karl Schilling).

According to the present invention very clear dyestuifs of the triarylmethane series capable of being chromed are made by condensing 1 molecular proportion of 5-hydroxy-benzene-1.2.4-tricarboxylic acid or 3-hydroxybenzene-1.2.4-tricarboxylic acid (hydroXy-trimellitic acid) or the equivalent amount of the corresponding anhydride with 2 molecular proportions of a cyclic meta-dihydroxy compound having a reactive hydrogen atom, for instance, by melting the reagents at a temperature between about 150 C.

and about 200 C. The dyestuffs may also be made by condensing, for instance, by'melting at a temperature between about 150 C. andv about 200 C., 1 molecular proportion of a benzoylben- ZOiC acid, which is obtainable by condensing 1 molecular proportion of one of the said 'hydroxytrimellitic acids with only 1 molecular proportion of a cyclic meta-dihydroxy compound having a reactive hydrogen atom, or of a halogenation product of such benzoylbenzoic acid, with 1 mol of a cyclic meta-dihydroxy compound having a reactive hydrogen atom. In this operation there may be used condensing agents as, for instance, concentrated sulfuric acid or para-toluenesulfonic acid, whereby a lower reaction temperature, for instance, between about 70 C. and about 140 C. may be applied. The product may be halogenated subsequently.

The new dyestufi's dye animal fibers in an acid bath very clear yellow to red tints; by afterchroming them the properties of fastness are considerably enhanced. The dyestufis are also suitable for chrome printing on cotton. The dyestuffs may also be chromed in substance whereby they are transformed into the corresponding chromium complex compounds which dye the fiber from an acid bath very clear shades which possess without after-chroming good fastness properties.

Germany March 27, 1936 The formation of the dyestuff probably occurs, for instance, as follows: a

coon 1 /COOH OH\ /OH 5 HOOC OH OH I The dyestuifs obtainable according to the process of the present invention are new. Therev are, for instance, obtained dyestufis of the following probable formula:

. HO\ 0 on 40 x o X X 0 X wherein the nuclei B may contain subs'tituents as, '50

for instance, hydroxy, methoxy, halogen, carboxy or sulfo or a condensed benzene nucleus in the positions X and wherein one Y represents hydroxy and the other Y hydrogen.

The same dyestuffs may also be characterized by one of the following formulae:

X/\/\ CM); X X

nooc

and

HO RKl OYTOH wherein the values R, X and Y have the aboveindicated meaning.

It is not known with certainty whether the hydroxy-trimellitic acids react in the manner presumed. It is also possible that isomerides of the above-mentioned compounds are formed having the constitution:

wherein the values R, X and Y have the aboveindicated meaning, or that the products are mixtures of isomerides of the said formulae.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts are by weight:

(1) 21 parts of 5-hydroxy-1.2.4-trimellitic anhydride and 22 parts of resorcinol are finely triturated and melted together. 7 parts of anhydrous zinc chloride are introduced into the mass, while stirring, and the whole is heated at 180 C. to 190 C. for 4 to 5 hours. During this time the melt solidifies. The mass is cooled and finely pulverized and then digested with 100 parts of hot hydrochloric acid of about 5 per cent. strength for some time. The undissolved yellow residue is filtered with suction while hot, dissolved in caustic soda solution, the solution is filtered and the yellow dyestufi is precipitated from the orange-red filtrate by means of dilute hydrochloric acid. For further purification the dyestuff may be recrystallized from aqueous alcohol. By dissolution in water with the necessary quantity of sodium bicarbonate and evaporation, the easily soluble orange-red sodium salt is obtained.

The dyestuff dyes animal fibers in an acid bath a very clear yellow tint; its properties of fastness are considerably enhanced by afterchroming.

(2) 39 parts of the yellow dyestuff described in Example 1 are suspended in 200 parts of glacial acetic acid and a solution of 34 parts of bromine in parts of glacial acetic acid is added, drop by drop, while stirring. When the bromine has been absorbed, the orange-yellow dyestufi is filtered with suction, washed with a small quantity of glacial acetic acid and then washed with a large quantity of water until neutral to Congo paper. The dyestufi may be recrystallized from a large quantity of hot glacial acetic acid or aqueous alcohol. It dyes wool in an acid bath orange-yellow tints the fastness of which is enhanced by after-chroming.

(3) 39 parts of the dyestuif described in Example 1 are suspended in 200 parts of glacial acetic acid and a solution of 68 parts of bromine in 100 parts of glacial acetic acid is added drop by drop while stirring. When the bromine has been absorbed, the dyestufi is isolated and purified as indicated in Example 2. The dyestuif has probably the following constitution:

or represents an isomeride thereof or a mixture of isomerides. It dyes wool in an acid bath a very clear yellowish red tint the fastness properties of which are considerably enhanced by after-chroming.

(4) 21 parts of 5-hydroxy-trimellitic anhydride, 31 parts of beta-resorcylic acid and 14 parts of anhydrous zinc chloride are triturated and heated at C. in an oil bath for several hours until the melt solidifies. After cooling, the crude product is pulverized and boiled with 200 parts of hydrochloric acid of 5 per cent. strength; the undissolved yellow dyestuff is filtered with suction while hot. It is dissolved in dilute sodium carbonate solution, yielding an orange-red solution with a green fluorescence; the solution is filtered and the dyestuff is precipitated by means of a dilute acid. For further purification the The dyestuif has probably the following constitution:

Hooo

wherein the number and the position of the bromine atom or atoms are unknown.

Perhaps it is an isomeride thereof or a mixture of isomerides. The dyestuff dyes animal fibers in an acid bath very clear yellowish red tints;

20 its fastness properties are considerably enhanced 35 dyestufi dyes wool in an acid bath yellow tints which, by after-chroming, become darker and faster.

(6) 16 parts of l.3-dihydroxy-naphthalene, 10 parts of 5-hydroxy-trimellitic anhydride and 4 parts of anhydrous zinc chloride are melted together as described in Example 5. The dyestufi is purified by boiling it with dilute hydrochloric acid, dissolving the insoluble residue in 250 parts of bicarbonate solution of 5 per cent. strength, filtering the solution and adding 60 parts of sodium chloride to the filtrate. After stirring for one hour the resulting dark precipitate is filtered with suction and the dyestuif is precipitated from the filtrate by means of dilute hydrochloric acid, washed with water and dried.

The dyestufi dyes animal fibers in an acid bath brown-red tints; the fastness properties are improved by aiter-chroming.

(7) 25 parts of pyrogallol, 21 parts of 5-hydroxy-trimellitic anhydride are melted together at 190 C. to 200 C. for 3 to 4 hours while excluding air. The pulverized melt is recrystallized from aqueous alcohol.

The dyestufi thus obtained has probably the 0 following constitution:

It may also be an isomeride of the above formula in which the positions of the ortho-situated hy- -75 droxyl and carboXyl groups are exchanged. The

dyestufi dyes wool in an acid bath red shades, which on after-chroming become violet and possess very good fastness properties.

(8) 42 parts of the dyestuff obtainable by condensation of 2 molecular proportions of pyrogal- 101 with 1 molecular proportion of -hydroxytrimellitic anhydride are suspended in 200 parts of glacial acetic acid.

While quickly stirring, a solution of 32 parts of bromine, in 100 parts of glacial acetic acid, is added drop by drop. After consumption of the bromine the dyestuiT is precipitated by means of water and recrystallized for purification from acetic acid of 50 per cent strength. It forms a red powder, which dissolves in bicarbonate solution to a red, and in caustic soda solution to a blue solution. The dyestufi probably possesses the following constitution:

oris an isomeride thereof or a mixture of isomerides. The dyestuff dyes wool in an acid bath wine-red shades. The after-chromed dyeings are violet and possess essentially better fastness properties than the non-chromed dyestuff.

(9) 32 parts of 2.4-dihydroXy-2-benz0ylortho-hydroxy-carboxy-l-benzoic acid having the following constitution:

HO on OOOH H0 on coon , OOOH I or a mixture of both isomerides (obtainable by condensation of one molecular proportion of 5- hydroXy-benzene-1.2.l-tricarboxylic acid with one molecular proportion of resorcinol, for instance, by heating the components at about C. to about C, in the presence of a solvent or diluent until the resorcinol is no longer detectable, or by treating the dyestuff of Example 1 with about 80 per cent. of caustic soda solution at about C. for about one hour), are melted together with 20 parts of resorcinol for 4 to 5 hours at C. The yellow melt is pulverized after cooling and dissolved in dilute caustic soda solution. The solution is heated to boiling and acidified with dilute hydrochloric acid. The yellow precipitate obtained is filtered with suction after cooling, washed until neutral and dried. The dyestufi' may be recrystallized, if desired, from aqueous alcohol. On dissolution in dilute alkalies and evaporation of the solution the easily soluble sodium salt of the dyestuff is obtained.

' The dyestufi dyes the animal fiber in an acid bath yellow shades. The fastness properties are essentially enhanced by after-chroming.

Instead of resorcinol there may also be used other meta-dihydroxy-compounds having a reactive hydrogen atom, as, for instance, chloro-, bromo-, nitro-, methyl-resorcinol or resorcinolmonomethyl ether and so on.

(10) By bromination of the dyestuff of Example 9, as indicated in Example 2, a dyestufi' is obtained which possesses similar properties as described therein. If the bromination is conducted as described in Example 3, a dyestufi is obtained which dyes wool in an acid bath very clear yellowish red shades, the fastness properties of which are essentially enhanced by afterchroming.

(11) 32 parts of 2'.4'-dihydroxy-2-benzoylortho-hydroxy-carboxyl-l-benzoic acid (cf. Example 9) and 17 parts of beta-resorcylic acid are introduced into about 20 parts of concentrated sulfuric acid and heated at 70 C. to 80 C. for about 6 hours, while stirring. Thereupon the mixture obtained is introduced into about 100 parts of water, the solution is saturated by means of sodium chloride and the yellow precipitateobtained is filtered with suction. In order to eliminate any unchanged 2'.4'-dihydroxy-2-benzoylortho-hydroxy-carboxy-l-benzoic acid from the yellow residue, it is stirred with about 25 parts of slaked lime and 250 parts of water and boiled again. After cooling the difiiculty soluble calcium salt of the dyestuff is filtered with suction, 40 washed with water and the yellow dyestufi is freed therefrom by means of dilute acids. With the condensation there occurs simultaneously sulfonation and the dyestuff possesses probably the following constitution:

' How o on 50 HOaS Hooo or is an isomeride thereof or a mixture of isomerides. The dyestufi dyes wool in an acid bath yellow shades. The fastness properties are essentially enhanced by after chroming.

On after-broming in alcohol or glacial acetic acid there are obtained dyestuffs the shades of which turn gradually red pari passu with the number of bromine atoms absorbed.

(l2) 16 parts of 2.4-dihydroxy-2-benzoyl- 65 (ortho-hydroXy-carboxy) -1-benzoic acid (cf. Ex-

ample 9) and 7.5 parts of pyrogallol are melted together at 160 C. to 170 C. for 4 hours while excluding air and stirring.

The pulverized melt is dissolved in sodium car- 70 bonate solution of 5 per cent. strength and filtered.

The red solution is heated to boiling and acidified with dilute hydrochloric acid until the reaction becomes feebly acid to Congo paper. After 75 standing for several hours the precipitated dyestuff is filtered with suction, washed with water several times and dried. The dyestuff dissolves in sodium carbonate or bicarbonate solution to a red, and in dilute caustic soda solution to a green solution. It dyes wool in an acid bath brown-red shades. The after-chromed dyeings show, according to the strength of the dyeing, grey to deeply black shades, the fastness of which is considerably enhanced compared with the nonchromed dyeings.

(13) 4.0 parts of 2'.4-dihydroxy-2-benzoyl- (ortho-hydroxy-carboxy) -1-benz0ic acid (of. EX- ample 9) and 20 parts of 1.3-dihydroxynaphthalene are heated at 150 C. to 160 C. for 4 hours. The pulverized melt is dissolved in bicarbonate solution and the solution obtained is boiled for half-an-hour with about 1 part of animal charcoal. The dyestuff is precipitated from the hot filtered yellow-red solution with dilute hydrochloric acid. After cooling entirely the dyestuff is isolated in the usual manner. For further purification it may be recrystallized from a large quantity of glacial acetic acid or dioxane. The dyestulf forms a yellow-red, indistinct crystalline powder. It dissolves in bicarbonate solution to a yellow-red solution having a yellow fluorescence. It dyes wool in an acid bath clear golden-yellow shades. The chromed dyeings are brown and show enhanced fastness properties.

(14) 24 parts of 2'.4-dihydroxy-2-benzoyl- (crtho-hydroxy-carboxy)-1-benzoic, acid, (cp. Example 9), parts of phloroglucin and 22 parts of para-toluene-sulfonic acid are heated at 120 C. to 130 C. for 3 to 4 hours. The pulverized melt is stirred with about 100 parts of water and the dyestufi is filtered with suction from the solution containing toluene-sulfonic acid. The dyestuff is dissolved in sodium carbonate solution, filtered, the red solution obtained is boiled with 1 part of animal charcoal, filtered, and the dyestuif is precipitated from the cooled solution by means of dilute hydrochloric acid. It dyes wool in an acid bath orange-yellow shades. On after-chroming essentially faster brown dyeings are obtained.

(15) 95 parts of 2'.4-dihydroxy-3'.5-dibro mo 2 benzoyl (ortho hydroxy carboxy) 1 benzoic acid, which is obtainable from the bromine-free compound (op. Example 9) by bromination in alcohol with the necessary quantity of bromine, 30parts of pyrogallol and 150 parts of para-toluene-sulfonic acid are melted together at 120 C. to 130 C. for about 4 hours while exeluding air. The cooled pulverized melt is stirred in 1000 parts of water and the dyestufi is filtered with suction. The brown-black residue is dissolved in sodium carbonate solution. The solution obtained is filtered and the dyestuff is precipitated therefrom by means of dilute hydrochloric acid. For further purification it may be recrystallized from acetic acid of 50 per cent. strength. The dyestufi dyes wool in an acid bath. On after-chroming it becomes black and the fastness properties are enhanced.

(16) 32 parts of 2'.4-dihydroxy-2-benzoyl- (ortho-hydroxy-carboxy)-1-benzoic acid and 16 parts of 4-chlororesorcinol are melted together at 160 C. to 170 C. for 4 hours. It is further worked up as described in the foregoing example. The dyestuff dyes wool in an acid bath orange-yellow tints. The after-chromed dying is brown and essentially faster.

(17) 31.8 parts of 2'.4'-dihydroxy-2-benzoylortho-hydroxy-carboxy-l-benzoic acid (cp. Example 9), 40 parts of the potassium salt of resorcinol-4.6-disulfonic acid and 27.0 parts of concentrated sulfuric acid are heated at 30 C. to 100 C. for about 2 to 10 hours. The condensation can also be efiected without heating, a longer time being necessary. The whole is then diluted with 1000 parts of water whereby the dyestufi" is precipitated. The dyestufi is filtered with suction, washed with water until neutral and may be recrystallized and purified by dissolution in dilute caustic soda solution, filtration and precipitation by means of dilute hydrochloric acid. The dyestuff forms a canary-yellow powder and possesses probably the following constitution:

(18) 31.8 parts of 2'.4'-dihydroxy-2-benzoylortho-hydroxy-carboxy-l-benzoic acid (cp. Example 9), 13.8 parts of 4-ethyl-resorcinol (cp. Berichte der Deutschen Chemischen Gesellschaft, vol. 47, page 54) and 2'7 parts of concentrated sulfuric acid are condensed under the conditions described in Example 17 and worked up as described therein. The dyestufi obtained forms a canary-yellow powder.

We claim: 1. The compounds of the general formula:

0H 0 on x c Y wherein X represents a member of the group consisting of hydrogen, bromine and sulfonic acid,

one Y represents amember of the group consisting of hydroxyl, carboxyl and alkyl, and the other Y represents hydrogen and the chromium complex compounds thereof.

2. The compound of the formula:

being a dyestufi which dyes wool from an acid bath red tints the fastness properties of which are essentially enhanced by after-chroming.

3. The compound of the formula:

being a dyestufi which dyes wool from an acid bath redtints the fastness properties of which are essentially enhanced by after-chroming.

4. The compound of the formula:

GEO/Ono]? Q H being a dyestufi which forms a canary-yellow powder and dyes wool from an acid bath yellow tints the fastness properties of which are essentially enhanced by after-chroming.

WILHELM ECKERT. KARL some. 

